US4436629A - Method for recovering useful products from waste products obtained when manufacturing aluminium fluoride - Google Patents

Method for recovering useful products from waste products obtained when manufacturing aluminium fluoride Download PDF

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Publication number
US4436629A
US4436629A US06/333,024 US33302481A US4436629A US 4436629 A US4436629 A US 4436629A US 33302481 A US33302481 A US 33302481A US 4436629 A US4436629 A US 4436629A
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hydroxide
silicoaluminate
sodium
aluminium
solution
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US06/333,024
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English (en)
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Lennart H. A. Berglund
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Boliden AB
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Boliden AB
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/48—Halides, with or without other cations besides aluminium
    • C01F7/50—Fluorides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/48—Halides, with or without other cations besides aluminium
    • C01F7/50—Fluorides
    • C01F7/54—Double compounds containing both aluminium and alkali metals or alkaline-earth metals

Definitions

  • the present invention relates to a method for recovering useful products from waste products obtained when producing aluminium fluoride from aluminium hydroxide and fluosilicic acid; and more particularly to recovering sodium silicoaluminates and sodium fluoroaluminates from silica waste, mother liquor and wash-water deriving from the manufacture of aluminium fluoride.
  • An object of the present invention is to obtain a possibility of recovering useful and economically valuable products from the waste products obtained in the aluminium fluoride production.
  • waste products constitute a serious environmental problem, even though they may be treated in the manner indicated before being deposited.
  • substantial amounts of silicon and fluorine are lost when the waste is treated in said manner.
  • SE,B, 366723 relates to a process to recover fluorine and aluminium from diluted, aqueous solutions, particularly mother liquors obtained in the crystallization of aluminium fluoride, whereby the mother liquors are treated with ammonia, ammonium dicarbonate to give a chiolite-analogous ammonium compound, [(NH 4 ) 5 Al 3 F 14 ].
  • the precipitation of said compound is carried out at pH 6-6.5.
  • SE,B, 7502835-7 relates to a concentrated synthetic fluxing agent based on calcium fluoride, where remaining fluorine quantities from the production of aluminium fluoride from fluosilicic acid and aluminiumhydroxide are precipitated using a calcium compound.
  • the present invention relates to a surprisingly distinctive method for recovering valuable substances in the form of useful products from waste of the aforedescribed kind, while at the same time substantially eliminating the environmental problems created by the waste.
  • the method according to the invention is also of economic interest, since, among other things, the waste need not be neutralized, meaning that no calcium hydroxide need to be used, which in turn means lower costs.
  • the present method is thus characterized by dissolving silica obtained in the manufacture of aluminium fluoride and contaminated with, inter alia, fluorine and aluminium, in a strongly basic hydroxide; mixing the first solution obtained with a second solution obtained by dissolving aluminium hydroxide with a strongly basic hydroxide, and with waste mother liquor and optionally also washing water from the manufacture of aluminium fluoride in such proportions that the pH-value of the mixture lies between about 10 and 14, the silica content of the waste products supplied being precipitated as a silicoaluminate, which is separated off, preferably by filtration, for optional further treatment or for direct use, whereafter fluorine, if present from the waste products, is recovered from the filtrate by adding thereto an aluminium compound in an amount sufficient to precipitate substantially all the fluorine content contained in the filtrate as a fluoroaluminate, which is separated off, preferably by filtration, for further use, and whereafter the final filtrate is passed to a recipient or utilized, for example, as process
  • the useful product produced in the first stage is a silicoaluminate, preferably a silicoaluminate of an alkali metal, such as sodium silicoaluminate.
  • a fluoroaluminate preferably sodium fluoroaluminate, which corresponds to cryolite.
  • Such products as sodium silicoaluminate, and sodium fluoroaluminate (cryolite) can be used directly, and are requested by the market.
  • sodium silicoaluminate can be used as a filler in the paper-making industry.
  • Sodium fluoroaluminate or cryolite is used to a large extent as a fluxing agent when producing aluminium electrolytically.
  • the useable products are recovered from the waste in sequential steps in a coherent process, in which first silicon and aluminium are recovered in the form of a silicoaluminate, preferably sodium silicoaluminate, and the fluorine content in an optional subsequent step is recovered, in the form of a fluoroaluminate, preferably sodium fluoroaluminate, i.e. cryolite.
  • the sodium silicoaluminate will precipitate practically instantaneously in the form of a very fine precipitate, which can readily be separated off from the mixture by filtration, e.g. by vacuum and/or pressure filtration. Subsequent to separating off this solid phase, it is slurried, suitably in warm water--together with a minor quantity of sodium hydroxide, in order to decompose any sodium fluoroaluminate which may have precipitated together with the sodium silicoaluminate. The suspension obtained is filtered off and the solid residual silicate product is dried. The alkaline washing water is suitably returned to the next precipitation cycle, in which sodium silicoaluminate is precipitated.
  • the filtrate obtained after precipitating the silicate content of the mixture contains the fluorine content of the waste products in the form of fluoride ions. If the fluoride content of the filtrate is so low that the filtrate can be deposited in its present form from an environmental point of view, the filtrate is passed to a suitable recipient. In the majority of cases, however, the fluorine content, in fluoride form, will be so high as to make depositing impermissable. When the fluorine-containing filtrate also contains sodium ions from the previous stage, the fluoride content can be precipitated out as cryolite, by adding an aluminium compound to the filtrate.
  • a suitable aluminium compound in this respect is aluminium sulphate, which is added in such an amount that all the sodium fluoride contained by the filtrate will precipitate out as sodium fluoroaluminate (cryolite).
  • the precipitate is filtered off and dried.
  • the filtrate which now contains minor quantities of sodium sulphate, can be discharged to a suitable recipient or used as process water in other processes.
  • a sodium silicate solution is prepared by supplying silica waste to a dissolver 1 through a conduit 2 and a 50%-sodium-hydroxide solution via a conduit 3 respectively, whereby alkaline washing water is charged simultaneously via the conduit 4b, to produce a pumpable silicate solution.
  • the silica waste dissolves rapidly at a temperature range of 70°-100° C.
  • a sodium aluminate solution by charging to a dissolver 5 through a conduit 6 aluminium hydroxide containing crystal water, and a 50%-sodium-hydroxide solution through the conduit 3, the temperature being adjusted to 90°-110° C.
  • the dissolver 5 is provided with a stirring means (not shown).
  • the sodium silicate solution from the dissolver 1 is passed through a conduit 7 to a mixer 8 provided with stirring means (not shown), while washing water and scrubbing water deriving from an aluminium fluoride plant is passed to the mixer through a conduit 9.
  • filtrate deriving from a subsequent stage can be charged to the mixer 8 through a conduit 4a.
  • the temperature of the liquid charged through conduit 7 is about 60° C., and hence no additional energy need to be supplied to the precipitating cycle.
  • sodium aluminate solution from the dissolver 5 is charged to said mixer 8 through a conduit 10, all silicate present immediately being precipitated as sodium silicoaluminate.
  • the reaction temperature should lie in a temperature range of 50°-100° C.
  • the fine-grain solid phase obtained is passed through a conduit 11 to a separation stage 12 employing pressure or vacuum filtration.
  • the separated filtrate is passed through a conduit 20 to a fluorine-recovery, or to a recipient, as shown by the dashed arrow 21.
  • the residual filter cake is dried by suction on the filter and then, as shown by arrow 13, passed to a subsequent washing stage 14, to which warm water (50° C.) may also be passed, as shown by arrow 15, and optionally entrained sodium fluoroaluminate is decomposed thereby while slurried with sodium hydroxide solution charged through a conduit 16.
  • the sodium hydroxide charge is increased and the temperature raised at the same time, there is obtained instead of an amorphous product a crystalline sodium silicate aluminate of the type Zeolite A.
  • the amorphous silicate product is passed to a separation stage 18 through a conduit 17, when the product is subjected to pressure or vacuum filtration and dried at 105° C., and is removed as a product, as shown by arrow 19.
  • the product can be removed in the form of a suspension containing about 30% dry substance.
  • a suspension of this nature can be used to advantage in partially replacing the titanium dioxide used in the paper-making industry as a filler material.
  • the filtrate resulting from the aforesaid slurrying and filtering operations is returned through conduits 4, 4b to the next sodium silicoaluminate precipitation process in the mixer 8, while a minor part is returned through conduits 4, 4a to be used in preparing sodium silicate solution in the dissolver 1.
  • the grain size of said product can be influenced as desired by charging aluminium sulphate to the mixer 8, sodium sulphate becoming present in the precipitate.
  • the grain size can also be influenced, however, by regulating the amount of hydroxide added to the washing stage 14 through a conduit 16.
  • the filtrate from stage 20 is passed to a mixer 22 through a conduit 20.
  • An aluminium sulphate solution is also charged to the mixer 22, through a conduit 23, said aluminium sulphate solution being charged in such an amount that all sodium fluoride present is precipitated as sodium fluoroaluminate, also known as cryolite. This precipitation preferably takes place at a pH-range of 8-10 and at a temperature of about 50° C.
  • the aluminium sulphate solution should contain approximately 8% Al 2 O 3 , at which concentration the solution can be stored without risk of solid aluminium sulphate crystallizing.
  • the pH-value of the mixture in the mixer 22 is excessive subsequent to charging the aluminium sulphate, the pH can be lowered by adding a minor quantity of sulphuric acid.
  • all of the contents of the mixer 22 are passed through a conduit 24 to a separation stage 25, in which a sodium fluoroaluminate product is separated off by pressure- or vacuum filtration.
  • the product is dried at a temperature of approximately 100° C., and is removed for retailing, as shown by the arrow 26.
  • the filtrate whose only impurity consists of minor quantities of sodium sulphate, is removed through a conduit 27 and passed to a recipient, or for use as process water in another process.
  • silica waste 130 grams were dissolved in 135 ml of a 50%-sodium hydroxide solution.
  • the silica waste contained, inter alia, 24.0% H 2 O, 66.0% SiO 2 , 3.27% F and 1.06% Al.
  • the silica waste dissolved at about 80° C.
  • a sodium aluminate solution by dissolving 362 g of aluminium hydroxide containing 10.3% of H 2 O in 400 g of 50%-sodium hydroxide at a temperature of about 100° C.
  • the mole ratio of Na 2 O/Al 2 O 3 was, in this case, 1.20.
  • the sodium silicate solution obtained was added to 2000 ml of liquid containing mother liquor, washing water and scrubbing water containing 22.9 F/l, 4.1 g Al/l and 5.4 g SiO 2 /l. Subsequent to this addition, the sodium aluminate solution was added, whereby the silicate content of the solution precipitated as sodium silicoaluminate. The precipitate was filtered off and dried by suction, and then slurried in 1000 ml of warm water, and any sodium fluoroaluminate which had precipitated together with the sodium silicoaluminate was decomposed during the slurrying process by adding 25 ml of a 50% sodium hydroxide solution.
  • an amorphous silicate product was separated off by pressure filtration, and dried at 105° C.
  • the sodium silicoaluminate product obtained had a weight of 250 g in a dry state, and contained, inter alia, 40% SiO 2 , 12% Na, 14% Al and ⁇ 0.2% F and 15% H 2 O and its brightness was measured as being 96%.
  • 165 ml of aluminium sulphate solution containing about 8% Al 2 O 3 were added to the filtrate, and the pH was adjusted to 8-10 by adding a minor quantity of sulphuric acid.
  • the sodium-fluoroaluminate precipitated obtained was separated off by pressure filtration and dried at about 100° C. 80 g of sodium fluoroaluminate (cryolite) containing, inter alia, 49% F, 32% Na, 13% Al, and 0.4% SiO 2 , were taken out.
  • cryolite obtained contained 54% F, 29.3% Na, 13% Al, and 0.4% SiO 2 .
  • Example 1 The procedure of Example 1 above was repeated except for an addition of CaCl 2 in the first stage, i.e. in the preparation of sodium silicoaluminate. Thereby calcium was added in an amount corresponding to twice the molar amount of phosphate present in the waste products. Thereby calcium phosphate was precipitated whereby the phosphate residue in the final cryolite product was decreased to less than 0.04%, approximately 0.02%.
  • the phosphate contents of the mother liquors are 50-100 mg of P 2 O 5 per liter.
  • calcium chloride has been used, but calcium hydroxide and calcium nitrate can be used as well.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Removal Of Specific Substances (AREA)
US06/333,024 1981-01-16 1981-12-21 Method for recovering useful products from waste products obtained when manufacturing aluminium fluoride Expired - Fee Related US4436629A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE8100218A SE430593B (sv) 1981-01-16 1981-01-16 Forfarande for att utvinna anvendbara produkter ur avfallsprodukter fran aluminiumfluoridframstellning
SE8100218 1981-01-16

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US4436629A true US4436629A (en) 1984-03-13

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US06/333,024 Expired - Fee Related US4436629A (en) 1981-01-16 1981-12-21 Method for recovering useful products from waste products obtained when manufacturing aluminium fluoride

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US (1) US4436629A (de)
EP (1) EP0056792B1 (de)
AT (1) ATE9986T1 (de)
CA (1) CA1183671A (de)
DE (1) DE3261009D1 (de)
SE (1) SE430593B (de)
WO (1) WO1982002538A1 (de)
YU (1) YU9282A (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5082608A (en) 1990-06-14 1992-01-21 Owens-Illinois Plastic Products Inc. Polystyrene foam sheet manufacture
US6235203B1 (en) * 1998-06-23 2001-05-22 Industrial Technology Research Institute Crystallization process for removing fluoride from waste water
CN112520770A (zh) * 2020-12-17 2021-03-19 河南中色东方韶星实业有限公司 一种大气冷凝料的综合利用方法

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE437015B (sv) * 1982-01-07 1985-02-04 Boliden Ab Forfarande for utvinning av anvendbara produkter fran avfallsprodukter herrorande fran framstellning av aluminiumfluorid
SE439477B (sv) * 1982-10-13 1985-06-17 Boliden Ab Forfarande for produktion av huvudsakligen ren kiselsyra fran avfallskiselsyra
SE453078B (sv) * 1986-09-09 1988-01-11 Alufluor Ab Forfarande for forbettring av cementbruks och betongs egenskaper
FR2930541B1 (fr) 2008-04-29 2010-05-21 Solvay Procede d'epuration de solutions aqueuses
EP2392857A1 (de) 2010-06-07 2011-12-07 L'Air Liquide Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Sauerstoff-Brennstoff-Brenner
CN110669933B (zh) * 2019-10-21 2021-04-27 金驰能源材料有限公司 一种去除镍钴锰溶液中氟的方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1594620A (de) * 1968-10-02 1970-06-08
AT315128B (de) * 1971-04-29 1974-05-10 Rudarsko Topionicarski Basen B Verfahren zur gleichzeitigen Gewinnung von Na3A1F6 und aktivem SiO2
DE2122647B2 (de) * 1971-05-07 1973-07-05 Lentia GmbH, Chem u pharm Erzeug msse Industriebedarf, 8000 München Verfahren zur rueckgewinnung von aluminium und fluor aus verduennten waessrigen aluminiumfluoridloesungen
CH601110A5 (de) * 1974-03-15 1978-06-30 Alusuisse
JPS5321399B2 (de) * 1975-03-25 1978-07-03

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5082608A (en) 1990-06-14 1992-01-21 Owens-Illinois Plastic Products Inc. Polystyrene foam sheet manufacture
US6235203B1 (en) * 1998-06-23 2001-05-22 Industrial Technology Research Institute Crystallization process for removing fluoride from waste water
CN112520770A (zh) * 2020-12-17 2021-03-19 河南中色东方韶星实业有限公司 一种大气冷凝料的综合利用方法
CN112520770B (zh) * 2020-12-17 2023-04-07 河南东方韶星实业有限公司 一种大气冷凝料的综合利用方法

Also Published As

Publication number Publication date
EP0056792A1 (de) 1982-07-28
SE430593B (sv) 1983-11-28
ATE9986T1 (de) 1984-11-15
SE8100218L (sv) 1982-07-17
CA1183671A (en) 1985-03-12
YU9282A (en) 1984-12-31
WO1982002538A1 (en) 1982-08-05
DE3261009D1 (en) 1984-11-29
EP0056792B1 (de) 1984-10-24

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